Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/84—Nitriles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/20—Vanadium, niobium or tantalum
  • B01J23/22—Vanadium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/26—Chromium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
  • C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene

Definitions

• the catalysts which have been so far proposed for the ammoxidation of alkyl-substituted aromatic compounds to produce aromatic nitriles include for example two-component catalysts such as those based on vanadium oxide and chromium oxide (Belgium Patent No. 632,702) and on oxides of antimony and vanadium (British Patent No. 1114898), as well as oxides of vanadium and chromium being incorporated with oxides of manganese, molybdenum, boron or cobalt (British Patent No. 1246108), uranium (Japanese Published Unexamined Patent Application laid-open as No.
• the catalysts mentioned above involve many problems left unsolved from a standpoint of industrial production such as necessity of using ammonia in fairly large excess of the stoichiometric quantity, reduced yields of aromatic nitriles and difficulty in temperature control of catalyst beds.
• reaction of aromatic compounds having many alkyl-substituents at relatively high concentrations makes it difficult to control the temperature of the catalyst bed and therefore increases, in some instance, the temperature of the catalyst bed up to 600° to 1000° C. or higher levels, resulting in extreme reduction in nitrile yields and simultaneously drastic deterioration of the catalytic activity.
• the present inventors conducted extensive research with a specific view to improving such disadvantages and, as a result, have succeeded in solving the above-mentioned problems by using as catalyst compositions containing oxides derived from (1) vanadium, (2) antimony and (3) at least one of uranium and chromium.
• the present invention relates to a method for producing aromatic nitriles which comprises reacting an alkyl-substituted aromatic compound with ammonia and oxygen in the presence of a catalyst containing, as the active components, oxides of (1) vanadium, (2) antimony and (3) at least one of uranium and chromium.
• the catalyst which is useful in the present invention, has, as the active components, compound oxides or mixed oxides of the elements shown under the above-mentioned oxides of (1), (2) and (3), whereby these are normally used in the state of being supported on a carrier.
• the catalyst, which is useful in the present invention is obtainable by the per se known method of preparing solid catalysts, and, for example, can be prepared by the following procedure.
• the catalyst can be prepared by dissolving a vanadium-containing compound, antimony-containing compound and uranium- and chromium-containing compound being convertible into oxides through chemical reaction or heating in a suitable solvent such as water, alcohol, acid and alkali, then impregnating them into, or precipitating them on a carrier, and calcining for example at 300° to 800° C.
• a suitable solvent such as water, alcohol, acid and alkali
• the above-mentioned vanadium-containing compound includes vanadium oxides (e.g. V 2 O 5 , V 2 O 4 , V 2 O 3 , etc.), vanadates (e.g. ammonium vanadate, vanadyl oxalate, vanadyl sulfate, vanadyl tartrate, etc.), and the like; as the antimony-containing compound there may be mentioned antimony oxides (e.g. Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , etc.), antimonic acids (e.g. orthoantimonic acid, metaantimonic acid, etc.), antimony halides and their partial hydrolyzates (e.g.
• the uranium-containing compound includes uranium oxides (e.g. UO 2 , U 3 O 8 , UO 3 , etc.), uranyl nitrate, uranyl acetate, uranyl chloride, etc., and the chromium-containing compound is chromium oxides (e.g.
• chromium slats chromium nitrate, chromium chloride, chromium oxalate, chromium tartrate, chromium sulfate, etc.; these can be all led easily into oxides.
• a formulating ratio for these vanadium-containing compound, antimony-containing compound and uranium- and chromium-containing compound is, per atom of vanadium, 0.1 to 10 of antimony, preferably 0.5 to 5, more preferably 1.0 to 3.0, and 0.01 to 5.0 of uranium, chromium, preferably 0.01 to 2.0, more preferably 0.02 to 1.0.
• the carrier use is preferably made of heat-resistant inorganic compounds such as alumina, silicon carbide, titanium oxide, silica, magnesia, diatomaceous earth, pumice, zirconium oxide, cerium oxide, calcium sulfate, titanium phosphate, silicon phosphate and their mixtures. Above all, alumina and titanium oxide are advantageously employed.
• the amount of the active components of the catalyst to be supported varies with types of carriers used, methods of preparing the catalyst, atomic ratios of the active components, etc. and, normally, is not less than 3 weight %, preferably not less than 10 weight %.
• the catalyst thus obtained shows high activity and selectivity of nitriles.
• alkyl-substituted aromatic compounds which are the starting material of the present invention, use is normally made of alkyl-substituted aromatic compounds in which the substituted alkyl groups have not more than 3 carbon atoms. Included among these are monoalkyl-substituted aromatic compounds such as ⁇ , ⁇ , ⁇ -picoline, 2-methyl-5-ethylpyridine, toluene, ethylbenzene, n-propylbenzene, cumene, ⁇ , ⁇ -methylnaphthalene and methylanthracene, dialkyl-substituted aromatic compound such as o-oxylene, p-xylene, m-xylene, o-, m-, p-ethyltoluene, o-, m-, p-isopropyltoluene, o-, m-, p-diethylbenzene, o-, m-, p-di
• oxygen-containing gas use is normally made of air, but oxygen or mixture of oxygen and air, mixture of air and carbon dioxide, mixture of air and steam and mixture of air and nitrogen may be utilized.
• the reaction temperature varies greatly with kind and mixing ratios of the starting gas, composition of the catalyst, types of the carrier, etc. and is normally 180° C. to 600° C., preferably 300° to 500° C.
• the starting gas and catalyst are desirably contacted normally at a space velocity (converted to NTP) in the range of 300 to 3000 (hr -1 ), preferably in the range of 400 to 2000 (hr -1 ).
• Unreacted alkyl-substituted aromatic compound and ammonia may be recirculated for use in some circumstances.
• benzonitrile from toluene, ethylbenzene, n-propylbenzene and cumene; o-tolunitrile, phthalonitrile and phthalimide from o-oxylene, o-isopropyltoluene, o-diethylbenzene and o-diisopropylbenzene; m-tolunitrile and isophthalonitrile from m-xylene, m-isopropyltoluene, m-diethylbenzene and m-diisopropylbenzene; p-tolunitrile and terephthalonitrile from p-xylene, p-isopropyltoluene, p-diethylbenzene and p-diisopropylbenzene; tricyanobenzene, dicyanomonomethylbenzene and monocyanodimethylbenzene and me
• the formed aromatic nitriles are cooled and collected directly as a solid, or are absorbed and collected in a suitable solvent, and can be made the aromatic nitriles with a higher degree of purity by means of some procedure such as distillation, although they are not particularly required to be purified.
• the present invention provides the advantages such as;
• the objective compound can be obtained in high yields, even when the mixing ratio of ammonia to an alkyl-substituted aromatic compound is reduced to a level in the neighborhood of the stoichiometric ratio (e.g. 1.0 to 1.5 moles of ammonia to 1 mole of an alkyl-substituted aromatic compound),
• the mixed solution consisting of resulted Sb(OH) 3 , 4.32 parts of CrO 3 , 5 parts of oxalic acid and 50 parts of water was added to the above uniform solution of V 2 O 5 , and 300 parts of fine powder of TiO 2 calcined at 800° C. was placed in the mixture while stirring well.
• the resulting mixture was stirred well over a water bath to evaporate a part of the water, and was made paste-formed, followed by wet-molding to a shape of 2 mm diameter ⁇ 5 mm length.
• V 2 O 5 To 7.85 parts of V 2 O 5 were added 65 parts of oxalic acid 200 parts of water, and the mixture was heated at about 100° C. over a water bath to prepare a uniform solution.
• 300 parts of 2-mm spheres of Al 2 O 3 calcined at 1200° C. was added to the solution, and the water was evaporated over a water bath to thereby impregnate the active components of catalyst on Al 2 O 3 carrier.
• an ammoxidation reaction was carried out by flowing a mixed gas consisting of 1 mole % of m-xylene, 4 mole % of ammonia and 95 mole % of air at a gas inlet pressure of 1.1 kg/cm 2 and a spece velocity of 2000 (hr -1 ) (converted to NTP), whereby the conversion of m-xylene was 100 mole %, with the isophthalonitrile yield (based on fed m-xylene) of 83.4 mole %.
• the temperature of the catalyst bed showed a distribution of maximum 41° C. deviated from the bath temperature.
• 1 l of the catalyst prepared thus was filled in the reactor as employed in Example 5 and, while maintaining the bath temperature at 429° C., an ammoxidation reaction was carried out by flowing a mixed gas consisting of 1 mole % of mesitylene, 7 mole % of ammonia and 92 mole % of air at a gas inlet pressure of 0.4 kg/cm 2 and a space velocity of 1200 (hr -1 ), whereby the conversion of mesitylene was 100 mole %, with 67.9 mole % of the yield of 1,3,5-tricyanobenzene (based on mesitylene fed).
• the temperature of the catalyst bed showed a distribution of maximum 31° C. deviated from the bath temperature, but the reaction temperature remained constant for a prolonged period of time.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Cited By (17)

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• 1980
  • 1980-04-01 JP JP4311980A patent/JPS56139444A/ja active Granted
• 1981
  • 1981-03-31 US US06/249,461 patent/US4336205A/en not_active Expired - Lifetime
  • 1981-03-31 CA CA000374312A patent/CA1144942A/en not_active Expired
  • 1981-03-31 AT AT81102431T patent/ATE9791T1/de active
  • 1981-03-31 DE DE8181102431T patent/DE3166547D1/de not_active Expired
  • 1981-03-31 EP EP81102431A patent/EP0037123B1/en not_active Expired

Patent Citations (6)

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